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SdngSiliconCarbidedngBetalmchtmang trongtnghpFischer-Tropsch
TS. Trng Hu Tr Trng i hc Bch khoa - i hc Nng GS.TS. Phm Hu Cng i hc Strasbourg (UdS) - Cng ha Php

Tm tt Qu trnh tng hp Fischer-Trospch ngy cng c quan tm nghin cu v ng dng nhiu trong sn xut nhin liu sch. Hiu qu ca qu trnh ny ph thuc rt nhiu vo vic s dng cht xc tc, cht mang, iu kin tin hnh phn ng Trong nghin cu ny, nhm tc gi trnh by kt qu v s dng coban trn cht mang silicon carbide dng beta v c hot ha bng ruthenium. Sn phm ca qu trnh tng hp Fischer-Trospch thu c c chn lc cao i vi cc hydrocarbon mch di (SC5+ 80% ) ngay c khi chuyn ha ln n 72%. Cc phng php phn tch ha l hin i cng c s dng trong nghin cu ny nhm nh gi cc c trng ca cht mang cng nh xc tc tng hp c.

1. Gii thiu chung Phn ng gia carbon monoxide (CO) v hydro (H2) vi s c mt ca cht xc tc to ra cc hp cht hydrocarbon (HC) c gi l qu trnh tng hp FischerTropsch. Phng trnh phn ng c trnh by nh sau: nCO + 2nH2 nCO + (2n+1)H2 CnH2n + nH2O CnH2n+2 + nH2O

Co thng c s dng khi mun to ra sn phm c t l HC cao [7]. Cht mang c th s dng l oxide nhm (Al2O3), oxide silica (SiO2), oxide titan (TiO2), zeolit (SBA-15, MCM-41), nano ng carbon (CTNs) [5 - 10]. Ngoi ra, mt s tc gi cn s dng kim loi qu (ruthenium, platin) lm cht kch hot cho xc tc [8, 10 - 12]. Trong nhng thp nin gn y, vi s tng gi khng ngng ca du m cng vi nhu cu v nhin liu sch tng mnh th qu trnh tng hp Fischer-Tropsch ngy cng c quan tm. Cc cng ty, tp on du kh nh: Sasol, Shell, Total u t nhiu d n ln vi quy m cng nghip Trung Quc, n , c, Australia, Canada, M [1, 3, 4]. Ngy nay, qu trnh tng hp FischerTropsch thng l mt cng on trong cc d n GTL (gas to liquid), CTL (charcoal to liquid), biomass [5, 7, 13]. y, ngun nguyn liu ban u l kh thin nhin, than, biomass c chuyn ha thnh kh tng hp (hn hp gia CO v H2), t chuyn thnh cc sn phm mong mun thng qua qu trnh tng hp Fischer-Tropsch. V vy, yu t c quan tm hng u trong qu trnh tng hp ny l chn lc i vi cc hydrocarbon (HC) c mch di t 5 nguyn t carbon tr ln (C5+). Trong phm vi bi bo ny, chng ti s trnh by mt s kt qu v qu trnh tng hp Fischer-Tropsch s dng cobalt (Co) lm pha hot tnh, ruthenium (Ru) lm cht kch hot v silicon carbide dng beta (-SiC) c cu trc t ong lm cht mang. y chng ti cng trnh by

Qu trnh ny c tng hp thnh cng vo nm 1923 v cng b ln u tin bi hai nh ha hc ngi c tn l Hans Fischer v Franz Tropsch vo nm 1926 [1]. Trong thc t, sn phm ca qu trnh ny rt a dng bao gm cc hydrocarbon no mch thng khng c nhnh (n-paraffin), c nhnh (i-paraffin), hydrocarbon khng no (olefin), cc hp cht cha oxy nh ru, acid acetic, aceton, methyl ethyl ketone [1]. Cc hp cht to ra t qu trnh ny tn ti c ba dng: kh, lng v rn vi s nguyn t carbon t C1 n C60 thm ch ln n trn C100. Sn phm ca qu trnh ny c s dng lm nhin liu (xng, diesel), cht bi trn, nguyn liu ban u trong cng ngh tng hp ha du [1, 2]. Mt trong nhng u im chnh ca qu trnh ny l to ra nhin liu sch hu nh khng cha lu hunh, nit, hp cht thm v cc kim loi. Qu trnh tng hp Fischer-Tropsch c th tin hnh trn nhiu loi xc tc khc nhau, pha hot tnh c s dng c th l cobalt (Co), st (Fe), niken (Ni) [1, 2, 5, 6], trong 34
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cc kt qu v nh gi cht mang, cht xc tc bng cc phng php ha l nh: xc nh b mt ring theo l thuyt BET (Brunauer - Emmett - Teller), kh xc tc theo chng trnh nhit (TPR), nhiu x tia X (XRD), knh hin vi in t qut (SEM). 2. Thc nghim 2.1. Tng hp xc tc 2.1.1. Nguyn vt liu ban u Tin cht ca pha hot tnh c s dng l mui nitrate cobalt (Co(NO3)2.6H2O)c tinh khit trn 99%. Tin cht ca cht kch hot l mui ruthenium clorua (RuCl3.nH2O). Cht mang c la chn c cu trc hnh t ong, c lm t vt liu silicon carbide dng beta (-SiC). Cht mang ny c cung cp bi Cng ty Sicat [14], c dng hnh tr vi cc thng s vt l: chiu cao 4cm, ng knh 2,54cm. 2.1.2. Qu trnh tng hp Xc tc c chun b bng phng php tm t theo cc cng on sau: + a pha hot tnh ln b mt cht mang: mui nitrate cobalt c ha tan trong nc ct, sau dng pipet a dung dch mui thm ln b mt cht mang. Tip theo, cht mang c tm dung dch mui s c sy kh. Qu trnh ny c lp li vi ln bo m ton b b mt xc tc c thm u. Qu trnh a cht kch hot ln b mt cht mang cng c thc hin theo quy trnh nh trn. + Sy kh: cht mang tm dung dch mui c a vo t sy kh 110Ctrong 14 gi. + Nung: qu trnh ny c thc hin 350C trong 2 gi trong khng kh nhm chuyn mui sang dng cc oxide tng ng. + Kh: qu trnh ny c thc hin 300C trong 4 gi trong dng kh H2 nhm chuyn oxide sang kim loi tng ng. 2.2. Cc phng php nh gi c trng ca cht mang v cht xc tc B mt ring cng s phn b kch thc ca mao qun c xc nh bng phng php hp ph ng nhit nit lng nhit - 196C, trn my Tristar 3.000. Cu trc tinh th ca pha hot tnh c xc nh bng phng php nhiu x tia X (XRD), qu trnh c thc hin vi gc qut 2 t 10 - 80o nh my D8 advance (hng

Bruker), s dng s pht x Cu K1 ( = 0,16 ) l ngun pht x tia X, thit b c trang b mt u d phn tn nng lng SOL-XE. Hnh thi b mt xc tc c o bng knh hin vi in t qut (SEM) trn my JEOL 6700FEG. Ngoi ra xc tc cn c kh theo chng trnh nhit (TPR) hiu r v qu trnh kh t cc dng oxide v kim loi tng ng. 2.3. Tng hp Fischer-Tropsch 2.3.1. H thng th nghim Qu trnh tng hp Fischer-Tropsch c tin hnh trn tng xc tc c nh c t trong thit b phn ng. y l thit b dng ng lng ng, ng knh trong ca ng pha trong l 2,54cm, ng knh ngoi ca ng pha ngoi l 10cm v chiu cao thit b l 50cm. Khong khng gian gia hai ng cho php cht ti nhit i qua nhm iu nhit cho thit b. Thit b phn ng c ni vi bnh iu nhit loi Huber (CC304) nhm n nh nhit thit b phn ng. Trong h thng ny, chng ti s dng cc thit b iu khin lu lng loi Brooks 5850, thit b iu chnh p in t loi Brooks 5835 nhm iu khin lu lng kh i vo v p sut trong ton b h thng. Ngoi ra, hai thit b ngng t cng c s dng phn chia dng sn phm thnh cc phn khc nhau nhm phc v cho qu trnh phn tch. o nhit trong mi trng phn ng, mt ng kim loi c ng knh ngoi 1,5mm (mt u kn) c thit k t tm ca thit b phn ng, ng ny cho php mt nhit k (ng knh 1mm, loi K) c th dch chuyn c bn trong ng o nhit nhiu v tr khc nhau. 2.3.2. Tng hp Fischer-Tropsch Qu trnh tng hp Fischer-Tropsch c tin hnh trn 10gram xc tc vi thnh phn 30%kl Co, 0,1%kl Ru. Kh tng hp c s dng c t l CO:H2 = 1:2. Trong qu trnh tin hnh tng hp, p sut ca qu trnh c gi khng thay i 40bar, nhng nhit iu khin trong bnh iu nhit c th thay i. Ngoi ra, do phn ng Fischer-Tropsch l phn ng ta nhit rt ln (H -165 kJ.mol-1), nn trnh nhit ca mi trng phn ng tng qu nhanh gy nguy him n h thng phn ng th dng kh i vo thit b phn ng s c lm long bng kh tr Argon (Ar). Dng sn phm sau khi i ra t thit b phn ng c a vo hai thit b ngng t. Nhit trong thit
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b th nht v th hai c gi 85oC v 15C. Dng kh khng ngng t i ra t hai thit b ny s c a vo phn tch my phn tch sc k kh (loi VARIAN CP3800). My ny c trang b hai detector, th nht l detector FID (Flame Ionisation Detector) cho php phn tch cc HC (C2-C9), cc hp cht cha oxy, th hai l detector TCD (Thermal Conductivity Detector) cho php phn tch kh tng hp (CO, H2), CH4 v CO2 (qu trnh ny c phn tch lin tc trong qu trnh tin hnh phn ng). Phn cht rn thu c trong thit b ngng t (sau khi dng th nghim) c phn tch bng my phn tch sc k SimDist (Simulated Distillation), y l my sc k loi VARIAN CP3800 c trang b h thng np mu PTV (Programmed Temperature Vaporisation). chuyn ha ca qu trnh c tnh trn nng CO i vo v i ra theo cng thc sau:

on hai s kh CoO v Co kim loi (qu trnh ny xy ra mc nng lng cao hn). Kt qu ny hon ton ph hp vi cc kt qu nghin cu c cng b bi nhiu tc gi [7, 8, 10, 12, 13]. Khi so snh kt qu ca chng ti vi kt qu cng b bi Maxime Lacroix cng cc cng s [2] trn cng hm lng cht xc tc (30%kl Co), trn cng loi cht mang (-SiC) cho thy khi c mt ca Ru th 2 nh (peak) xut hin nhit thp hn (khong 280C v 350C so vi 310C v 380C). Theo kt qu cng b bi Jingping Hong cng cc cng s [8], vic kch hot xc tc bng Ru s to ra s thay i ng k ln qu trnh kh, ng thi gia tng mc phn tn ca Co trn b mt cht mang. T nhng kt qu thu c nghin cu qu trnh kh xc tc theo chng
Bng 1. Cc c trng ca cht mang v cht xc tc o bng phng php hp ph nit lng

chn lc i vi HC mch di c tnh theo tng lng HC thu c t 2 my phn tch (CO2 v cc hp cht cha oxy c hm lng nh (< 0,5%)) theo cng thc sau: SC5+ = 100 - (SC1 + SC2 + SC3 + SC4) 3. Kt qu v tho lun 3.1. c trng ca cht mang v cht xc tc B mt ring tnh ton theo l thuyt BET cng ng knh trung bnh v th tch ca mao qun c trnh by Bng 1; s phn b kch thc mao qun c trnh by Hnh 1. Kt qu ny cho thy khi a xc tc ln b mt cht mang th mt phn xc tc i vo trong cc mao qun dn n b mt ring, kch thc trung bnh cng nh th tch ca mao qun ca xc tc thu c gim i so vi cht mang ban u. Trn gin phn b kch thc ca mao qun cho thy trong cht mang cng nh xc tc tng hp c khng c cc mao qun c kch thc vi xp (micropore), kch thc ca mao qun phn b trong khong 3 - 130nm. T kt qu ca qu trnh kh xc tc theo chng trnh nhit c trnh by trn Hnh 2 cho thy qu trnh chuyn t oxide cobalt v cobalt kim loi xy ra trong khong nhit t 220 - 480C. Qu trnh ny gm hai giai on (tng ng vi hai nh (peak) trn gin ), giai on u l qu trnh kh Co3O4 v CoO (qu trnh ny xy ra mc nng lng thp), cn giai 36
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Hnh 1. S phn b ng knh ca mao qun trong cht mang v xc tc

Hnh 2. Gin kh xc tc theo chng trnh nhit (TPR)

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trnh nhit cho php, chng ti la chn qu trnh kh nhit thp (300C) trong thi gian di (4 gi) nhm mc ch thu c xc tc c phn tn ng u (xem hnh nh thu c t knh hin vi in t qut Hnh 4). Kt qu chp nhiu x tia X c trnh by trn Hnh 3 cho thy trong iu kin kh xc tc nh nu trn (mc 2.1.2) th ton b oxide cobalt c kh v dng kim loi. Trn gin nhiu x tia X thu c, chng ti khng thy s xut hin nh (peak) ca Ru. iu ny c

th gii thch do hm lng ca Ru qu nh so vi hm lng ca Co. Hnh thi b mt xc tc thu c t knh hin vi in t qut c trnh by trn Hnh 4 cho thy xc tc c phn b kh ng u trn b mt cht mang, kch thc ca ht xc tc ln hn 100nm v tn ti ch yu dng tp hp ca nhiu ht. 3.2. Kt qu ca qu trnh tng hp Fischer-Tropsch nh gi hot tnh ca xc tc tng hp c, nhm tc gi tin hnh hai th nghim; trong mi th nghim, mi iu kin phn ng th qu trnh tng hp c tin hnh trong thi gian t 24 - 48 gi nhm xem xt n nh ca xc tc. Kt qu t hai th nghim u cho thy hot tnh ca xc tc vn n nh sau hn 100 gi lm vic. Bng 2 trnh by cc kt qu thu c t 2 th nghim ny. Trong th nghim th nht, khi GHSV (Gas Hourly Space Velocity) khng thay i, tng nhit iu khin hay nng ca kh tng hp i vo thit b phn ng th chuyn ha tng ln. th nghim th hai, khi nhit iu khin khng thay i, nng ca kh tng hp tng dn (kh Argon gim dn hay GHSV gim dn) th chuyn ha cng tng ln.

Hnh 3. Gin nhiu x tia X (XRD)

S tng chuyn ha ny c th c gii thch do s tng p sut ring phn ca kh tng hp trong mi trng phn ng dn n s tng kh nng khuch tn cht phn ng n cc tm xc tc. Mt khc, khi GHSV gim th thi gian lu ca kh tng hp trong mi trng phn ng hay thi gian tip xc gia cht phn ng vi cht xc tc tng ln, cng c th l l do lm tng chuyn ha. iu ny c th nhn thy khi so snh kt qu t hai th nghim trong cng iu kin v nhit iu khin v thnh phn kh i vo thit b phn ng, khi Hnh 4. Hnh nh thu c t knh hin vi in t qut (SEM) tc GHSV gim i 50% Bng 2. Kt qu ca qu trnh tng hp Fischer - Trospch trn xc tc 0,1%Ru.30%Co/-SiC (t 2.400 th nghim th hai n 1.200 th nghim th nht) th chuyn ha tng ln mt cch r rt (t 47 - 66%). Thc t, c th khng nh c l do lm thay i chuyn ha trong nhng trng hp ny th cn phi c thm nhiu nghin cu kha cnh ng hc ca phn ng. Kt qu t hai th nghim ny cng cho thy xc tc tng hp c c chn lc SC5+
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cao ngay c khi chuyn ha ln n 72%. Trong c hai th nghim, chn lc hu nh khng thay i khi thay i iu kin th nghim. Vi nhng kt qu thu c ban u nghin cu ny th vic gii thch v n nh ca chn khi chuyn ha thay i l rt kh khn. Tuy nhin, chng ti cho rng yu t nh hng n chn lc trong qu trnh tng hp Fischer-Tropsch trc ht ph thuc nhiu vo kch thc mao qun [7, 8, 15]. Xem xt kt qu t nhng nhm nghin cu ny cho thy, khi kch thc mao qun tng t 2,7 - 2,9nm [7] n 6 - 10nm [8] th chn lc tng t 53 - 86%. Tuy nhin, nghin cu ca Jingping Hong cng cc cng s [8] cng cho thy khi kch thc mao qun tng ln n 16nm th chn lc li gim xung. Ngoi ra, kt qu thu c khi o dn nhit ca vt liu -SiC dng cu trc t ong th David Edouard cng cc cng s [16] cho thy y l loi vt liu c kh nng dn nhit. V vy, mc d khi chuyn ha tng ln, lng nhit ta ra ln hn nhng khi s dng cht mang -SiC th kh nng trao i nhit vi cht ti nhit ca h thng tt hn nn hn ch c cc im nng cc b trn b mt xc tc, do c th trnh c s b gy cc mch HC di to thnh trc . Khi so snh kt qu ny vi kt qu c cng b bi Haifeng Xiong cng cc cng s [11] trn cng hm lng cht kch hot v cht xc tc (0,1%kl Ru, 30%kl Co) cho thy, khi s dng cht mang SBA-15 cho chn lc cao hn khong 5% nhng chuyn ha trong trng hp ny rt thp (35,4%) so vi 47 - 72% trong trng hp s dng -SiC. Tuy nhin, cn phi nhn mnh iu kin tin hnh th nghim trong hai trng hp ny khng ging nhau. Trong thc t, vic nghin cu s nh hng ca cht mang cng nh cht kch hot ln chuyn ha v chn lc khi s dng cobalt trong tng hp FischerTropsch c nghin cu v cng b bi nhiu tc gi

[8, 10, 12, 13]. Song do s a dng ca cht mang, hm lng cht xc tc, loi cht kch hot s dng, dng thit b phn ng cng nh iu kin tin hnh th nghim (p sut, nhit , thnh phn kh, GHSV) nn vic so snh kt qu gia cc nhm tc gi rt kh thc hin. Mt s kt qu cng b cho thy, vic s dng ruthenium lm cht kch hot tng chuyn ha CO [11, 12], nhng chn lc th ph thuc vo hm lng ruthenium a vo xc tc, vi hm lng thp (0,05 - 0,1%) th chn lc tng ln [11], ngc li vi hm lng cao (1 - 4%) th chn lc gim xung [12]. Vic gim chn lc trong trng hp ny c th c gii thch l khi hm lng ruthenium tng ln th vn tc phn ng tng ln tc l qu trnh hydro ha tng nhanh. Khi , cc gc hydro t do nhanh chng tn cng ln cc gc hydrocarbon lm ngt mch phn ng to ra sn phm. Ngoi ra, khi vn tc tng nhanh th nhit trong vng phn ng rt ln c th dn n vic b gy cc HC mch di to thnh trc . Hnh 5 trnh by mt trong nhng kt qu v s phn b HC thu c trong sn phm ca qu trnh. Kt qu ny cho thy, khi lm vic iu kin p sut cao (40 bar) th trong thnh phn ca sn phm thu c hm lng cc HC rn (C18+) chim mt t l cao (> 50%kl) khi so snh vi cc kt qu thu c p sut thp hn (20, 25 bar) [17 - 19]. Ngoi ra, th ny cng cho thy s gim st bt thng hm lng cc HC t C4 - C8, iu ny c th do s mt mt. Thc t, cc HC t C1 - C9 c phn tch lin tc trong qu trnh tin hnh phn ng. , p sut trong h thng rt cao (40 bar) nn mt phn kh C1 - C9 b hp ph trong phn HC nng hn, khi dng phn ng thu hi phn rn th p sut trong h thng gim dn v p sut mi trng. Trong qu trnh ny, nhng HC nh s bay hi nn s khng xut hin trong kt qu phn tch trn my phn tch sc k Sim Dist. S mt mt cc HC h thng ny c th lm gim nh gi tr chn lc tnh ton c t cc kt qu phn tch. 4. Kt lun Chng ti thnh cng trong vic tng hp xc tc 0,1%kl Ru v 30%kl Co trn cht mang -SiC v nh gi cc c trng ca xc tc bng cc phng php phn tch ha l hin i nh: BET, TPR, XRD, SEM. S dng xc tc tng hp c trong vic tng hp Fischer-Tropsch cho thy loi cht mang -SiC dng cu trc t ong c n nh, hot tnh cao, chn lc SC5+ cao ngay c khi chuyn ha ln n 72%.

Hnh 5. S phn b HC thu c t th nghim th nht

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Zhengc and Dongge Tong. The nature of cobalt species in carbon nanotubes and their catalytic performance in Fischer-Tropsch reaction. J. Mater. Chem. Rev 2009; Vol 19: p. 9241 - 9249. 10. Heline Karaca, Pascal Fongarland, Anne GribovalConstant, Andrei Y. Khodakov, Kai Hortmann, Sander Van Donk. Intergranular and intragranular cobalt repartitions in aluminasupported FischereTropsch catalysts promoted with platinum, C. R. Chimie. 2009; Vol 12: p. 668 - 676. 11. Haifeng Xiong, Yuhua Zhang, Kongyong Liew, Jinlin Li. Ruthenium promotion of Co/SBA-15 catalysts with high cobalt loading for Fischer-Tropsch synthesis. Fuel Processing Technology 2009; Vol 90: p. 237 - 246. 12. Yu-Ping Li, Tie-Jun Wang, Chuang-Zhi Wu, XinXin Qin, Noritatsu Tsubaki. Effect of Ru addition to Co/SiO2/ HZSM-5 catalysts on Fischer-Tropsch synthesis of gasolinerange hydrocarbons. Catalysis Communications. 2009; Vol 10: p. 1868 - 1874. 13. Wei Chu, Petr A. Chernavskii, Lon Gengembre, Galina A. Pankina, Pascal Fongarland, Andrei Y. Khodakov, 2007. Cobalt species in promoted cobalt alumina-supported Fischer-Tropsch catalysts. Journal of Catalysis. Vol 252: p. 215 - 230. 14. http://www.sicatcatalyst.com 15. Dechen Song, Jinlin Li. Effect of catalyst pore size on the catalytic performance of silica supported cobalt Fischer-Tropsch catalysts. Journal of Molecular Catalysis A: Chemical 2006. Vol 247: p. 206 - 212. 16. David Edouard, Tri Truong Huu, Cuong Pham Huu, Francis Luck, Daniel Schweich. The effective thermal properties of solid foam beds: Experimental and estimated temperature profiles. International Journal of Heat and Mass Transfer 2010. 53 (19 - 20): p. 3807 - 3816. 17. R. de la Osa, A. De Lucas, A. Romero, J.L. Valverde, P. Snchez. Influence of the catalytic support on the industrial Fischer-Tropsch synthetic diesel production. Catalysis Today. 2011; Vol 176: p. 298 - 302. 18. Ahmad Tavasoli, Reza M. Malek Abbaslou, Ajay K. Dalai. Deactivation behavior of ruthenium promoted Co/g-Al2O3 catalysts in Fischer-Tropsch synthesis. Applied Catalysis A: General. 2008; 346: p. 58 - 64. 19. Wei Liu, Jianli Hu, Yong Wang. Fischer-Tropsch synthesis on ceramic monolith-structured catalysts. Catalysis Today. 2009; Vol 140: p. 142 - 148.

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